JP5527377B2 - Flame retardant and inorganic-organic composite flame retardant composition - Google Patents

Description

  The present invention relates to a flame retardant and an inorganic-organic composite flame retardant composition.

In recent years, flame retardant materials have been widely used in fields such as electronic materials and building materials. Flame retardant materials are usually prepared by blending a flame retardant with a resin. Examples of such flame retardants include halogen compounds, antimony trioxide, phosphorus compounds, inorganic hydroxides (hydrated metal compounds, etc.) )It has been known.
The use of halogenated compounds and antimony trioxide has been restricted in recent years because there are concerns about the impact on the environment such as destruction of the ozone layer and generation of dioxins. Phosphorus compounds are refrained from their use because of their high unit cost and increased production costs.
On the other hand, inorganic hydroxides are considered to be particularly useful as flame retardants because they have the property of being relatively incombustible and are inexpensive and environmentally friendly.

However, when an inorganic hydroxide is used as a flame retardant, it must be blended in a larger amount than an organic flame retardant in order to obtain the same flame retardant effect as an organic flame retardant compound. For this reason, it is extremely important to improve the affinity between the polymer material and the inorganic hydroxide. From such a viewpoint, many surface modification treatment methods for inorganic hydroxides have been performed.
One of the most widely used surface modification treatment methods is a method of coating the surface of an inorganic hydroxide with an organic compound. In this method, the adhesion of the organic compound to the inorganic hydroxide surface becomes important.
In an inorganic hydroxide having a functional group, a strong coating layer can be formed by using a compound having a substituent that can react with the functional group (such as a hydroxyl group), such as a silane coupling agent (Patent Document 2). : JP-A 61-275359, Patent Document 3: JP-A 63-258958).

However, the conventional flame retardant comprising the inorganic hydroxide subjected to the surface treatment still has various problems as described below.
(1) Problems in electrical properties Since the inorganic hydroxide itself has a high dielectric constant, the dielectric constant of the molded product is increased by adding a large amount of the inorganic hydroxide.
The dispersibility of the inorganic hydroxide is insufficient, and in order to improve this, it is necessary to add a dispersant such as colloidal silica, but the addition also increases the dielectric constant of the molded product.
Migration resistance and insulation reliability are reduced by adding inorganic hydroxide.
(2) Problems in mechanical properties When a large amount of inorganic hydroxide having insufficient affinity with the resin is added, the molded product becomes brittle.
Since the dispersibility of the inorganic hydroxide is insufficient, it is difficult to highly fill the resin with an inorganic substance.

(3) Problems in acid resistance and alkali resistance Depending on the type of inorganic hydroxide, it originally has the property of low acid resistance and alkali resistance. Therefore, the composition to which an inorganic hydroxide is added as a flame retardant has insufficient acid resistance and alkali resistance. In addition, in applications for electronic materials, acid resistance is an essential property during etching processing.
(4) Problems in thermal properties The dispersibility of the inorganic hydroxide is insufficient, and the heat resistance is lowered by the addition of a dispersant or the use of an inorganic surface treatment agent to improve this.
(5) Problems in flame retardancy The dispersibility of the inorganic hydroxide with respect to the resin is insufficient, it is difficult to fill the resin in a high amount, and sufficient flame retardancy cannot be provided.
Since the flame retardant effect is proportional to the specific surface area of the inorganic hydroxide, the flame retardant effect is reduced when the resin is not sufficiently dispersed in the resin and agglomerated.
The dispersibility of the inorganic hydroxide is insufficient. In order to improve this, the addition of a dispersant or the use of an inorganic surface treatment agent lowers the flame retardancy.

  As described above, considering the deterioration of mechanical properties, electrical properties, chemical properties, etc. of molded products, there is a limit to the amount of inorganic hydroxide that can be filled in the resin, and sufficient flame retardancy is required. It is difficult to demonstrate.

Japanese Patent Laid-Open No. 5-230279 JP 61-275359 A JP-A 63-258958

  The present invention has been made in view of such circumstances, and even when the resin is highly filled, it is difficult to highly disperse and to suppress deterioration of electrical properties, mechanical properties, and the like of the obtained molded product. It aims at providing the inorganic-organic composite flame-retardant composition comprised including a flame retardant and this flame retardant and organic resin.

  As a result of intensive studies to achieve the above object, the present inventors have found that a flame retardant formed by forming a predetermined carbodiimide group-containing organic layer on the surface of the inorganic hydroxide is highly filled in the resin. Highly dispersed, can suppress deterioration of electrical properties (increased dielectric constant, migration resistance), mechanical properties (become brittle), and thermal properties It was found that sufficient flame retardancy can be imparted to the present invention and the present invention has been completed.

That is, the present invention
[1] An inorganic hydroxide and a carbodiimide group-containing organic layer chemically bonded to the surface of the inorganic hydroxide, wherein the carbodiimide group-containing organic layer is a carbodiimide group-containing compound represented by formula (1), and A flame retardant comprising at least one carbodiimide group-containing compound represented by formula (2),
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -NCO] l (1)
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -A-Z- (X 2) 3] l (2)
[Wherein, R ¹ represents a residue from an isocyanate compound, and X ¹ and X ² are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may contain an unsaturated structure. Represents a C 6-20 aryl group, a C 7-20 aralkyl group, or a C 1-20 alkoxy group, and when X ¹ and X ² are plural, they may be the same as or different from each other; Z represents a silicon atom or a titanium atom independently of each other, A represents a divalent or higher valent organic group containing a bond derived from an isocyanate group, m and l satisfy 1 to 3 and m + 1 = 4 An integer is represented, and n represents an integer of 1 to 100. ]
[2] When tetrahydrofuran is used as a dispersion medium, the standard deviation (A ₁ ) of the particle size distribution of the untreated inorganic hydroxide and the particle size distribution of the inorganic hydroxide provided with the carbodiimide group-containing organic layer The standard deviation (A ₂ ) of [1] satisfies the following formula:
(A ₂ ) / (A ₁ ) ≦ 1.0
[3] When tetrahydrofuran is used as a dispersion medium, the volume average particle diameter (M ₁ ) of the surface untreated inorganic hydroxide and the volume average particle diameter of the inorganic hydroxide provided with the carbodiimide group-containing organic layer ( M ₂ ) satisfies the following formula: [1] flame retardant,
(M ₂ ) / (M ₁ ) ≦ 1.0
[4] When using pH 7 water as a dispersion medium, the standard deviation (A ₃ ) of the particle size distribution of the surface untreated inorganic hydroxide, and the inorganic hydroxide particles comprising the carbodiimide group-containing organic layer The flame retardant of [1], wherein the standard deviation (A ₄ ) of the diameter distribution satisfies the following formula:
(A ₄ ) / (A ₃ )> 1.0
[5] Volume average particle diameter (M ₃ ) of surface untreated inorganic hydroxide and pH average inorganic hydroxide provided with the carbodiimide group-containing organic layer when pH 7 water is used as a dispersion medium [1] flame retardant having a diameter (M ₄ ) satisfying the following formula:
(M ₄ ) / (M ₃ )> 1.0
[6] The flame retardant according to [1], wherein at least one terminal isocyanate group of the carbodiimide group-containing compound represented by the formula (1) is sealed with a functional group having reactivity with the isocyanate group,
[7] The flame retardant according to [6], wherein the functional group having reactivity with the isocyanate group is a hydroxyl group, a primary or secondary amino group, a carboxyl group, or a thiol group.
[8] The flame retardant according to any one of [1] to [7], wherein the inorganic hydroxide is particles having a volume average particle diameter of 1 nm to 100 μm.
[9] The flame retardant according to any one of [1] to [8], wherein the carbodiimide group-containing organic layer is lipophilic.
[10] An inorganic-organic composite flame retardant composition comprising the flame retardant according to any one of [1] to [9] and an organic resin,
[11] The inorganic-organic composite flame retardant composition according to [10], wherein the flame retardant is contained in an amount of 15% by mass or more based on the organic resin.
[12] The inorganic-organic composite flame retardant composition according to [10] or [11], wherein the flame retardant contained in 1 g of the composition has a total surface area of 2000 cm ² or more.

The flame retardant of the present invention is excellent in affinity and dispersibility with an organic resin and an organic solvent because the inorganic hydroxide surface is covered with a predetermined carbodiimide group-containing organic layer, and the organic resin and the carbodiimide group are chemically A strong bond is possible because of the reaction. For this reason, even when this flame retardant is highly filled in an organic resin, it is possible to suppress a decrease in mechanical strength of the obtained molded product and a decrease in electrical properties such as migration resistance.
In addition, since the flame retardant of the present invention is excellent in dispersibility in organic resins and organic solvents, it is not necessary to use a dispersant in combination with an increase in dielectric constant caused by the dispersant as in conventional products, and heat resistance. , Flame retardant deterioration can be prevented.
Thus, if the flame retardant of the present invention is used, even if the amount of addition is increased, the physical, electrical, thermal, and chemical properties of the resulting molded article can be suppressed from decreasing. Various inorganic hydroxide addition effects such as a reduction in the coefficient of thermal expansion can be effectively imparted to the molded article.

Hereinafter, the present invention will be described in more detail.
The flame retardant according to the present invention includes an inorganic hydroxide and a predetermined carbodiimide group-containing organic layer chemically bonded to the surface of the inorganic hydroxide.
The inorganic hydroxide in the present invention is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, nickel hydroxide, chromium hydroxide, iron hydroxide, hydroxide Although copper etc. are mentioned, it is preferable to use aluminum hydroxide, magnesium hydroxide, potassium hydroxide, and calcium hydroxide because it is widely used as a flame retardant and is easily available. In particular, it is preferable to use magnesium hydroxide and / or aluminum hydroxide which is generally used as a flame retardant.

  Although the shape of the inorganic hydroxide differs depending on the use of the composition, it cannot be specified unconditionally, but it is flame retardant that is proportional to the dispersibility of the inorganic hydroxide in the composition, the moldability of the composition, and the specific surface area. In view of the effect of improving the property (“polymer flame retardant technology” (CMC Publishing)), etc., the volume average particle diameter is 1 nm to 100 μm, preferably 10 nm to 50 μm, more preferably 20 nm to 30 μm. Is preferred.

The carbodiimide group-containing organic layer in the present invention includes a carbodiimide group-containing compound.
In this case, the carbodiimide group-containing compound is not limited as long as it has a carbodiimide group, and for example, a compound represented by the following formula (I) can be used.
^{OCN- (R 1 -N = C =} N) n -R 1 -NCO (I)
(R ¹ represents a residue from an isocyanate compound, and n represents an integer of 1 to 100.)

A compound having a carbodiimide group represented by the formula (I) (hereinafter sometimes simply referred to as “carbodiimide compound”) can be obtained from an organic polyisocyanate compound in the presence of a catalyst that promotes carbodiimidization of isocyanate. Specifically, for example, the method disclosed in JP-A-51-61599, the method of LM Alberino et al. (J. Appl. Polym. Sci., 21, 190 (1990)), JP-A-2- The carbodiimide compound which can be manufactured by the method etc. which are indicated by 292316 gazette can be mentioned.
The weight average molecular weight of the carbodiimide compound represented by the formula (I) is generally about 200 to 100,000, but 500 to 50,000 is preferable in consideration of dispersibility in an organic resin and an organic solvent.

  Examples of the organic isocyanate compound used in the production of the carbodiimide compound include 4,4′-dicyclohexylmethane diisocyanate, m-tetramethylxylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, A mixture of 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, crude tolylene diisocyanate, crude methylene diphenyl diisocyanate, 4,4 ′, 4 ″ -triphenylmethylene triisocyanate, xylene diisocyanate, hexamethylene-1, 6-diisocyanate, lysine diisocyanate, hydrogenated methylene diphenyl diisocyanate, m-phenyl diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-biphenylene diiso Anate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, etc. The species can be used alone or as a mixture of two or more species. Among these, considering reactivity and dispersibility in resin, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, hexamethylene-1,6-diisocyanate, m-tetramethylxylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate is preferred.

Polycondensation occurs by carbodiimidizing the isocyanate group in the organic isocyanate compound. This reaction is usually performed by heating the organic isocyanate compound in the presence of a carbodiimidization catalyst. In this case, a functional group having reactivity with an isocyanate group at an appropriate stage, for example, a compound having a hydroxyl group, a primary or secondary amino group, a carboxyl group, or a thiol group is added as a terminal blocker, and a carbodiimide compound The molecular weight (degree of polymerization) of the obtained carbodiimide compound can be adjusted by sealing the end of the carbodiimide. The degree of polymerization can also be adjusted by the concentration of the isocyanate compound and the reaction time.
Various examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl- 2-phospholene-1-oxide, these 3-phospholene isomers and the like are suitable in terms of yield and other aspects.

Although the said reaction can also be performed in absence of a solvent, you may carry out in solvent presence. In addition, a solvent can also be added during the reaction.
The solvent is not particularly limited as long as it does not affect the isocyanate group and carbodiimide group during the reaction, and a solvent corresponding to the polymerization method may be appropriately selected.
Specific examples of usable solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; pentane, 2-methylbutane, and n-hexane. , Cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane, Aliphatic or aromatic hydrocarbons such as methylcyclohexane, ethylcyclohexane, p-menthane, benzene, toluene, xylene and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chlorobenzene and tetrabromoethane Elements; ethers such as ethyl ether, dimethyl ether, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; sulfur and nitrogen-containing organic compounds such as nitropropene, nitrobenzene, pyridine, dimethylformamide and dimethyl sulfoxide . These may be used alone or in combination of two or more.

  Furthermore, when the carbodiimide compound terminal is sealed with an end-capping segment, which will be described later, and hydrophilized, in addition to the above solvent as a diluent, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1- Hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl Alcohol, alcohol such as cyclohexanol ; Methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, ether alcohols such as diethylene glycol monobutyl ether can also be used. These may be used alone or in combination of two or more. However, since the reactivity of the carbodiimide group is high, the dilution is preferably performed at a relatively low temperature.

Moreover, in the flame retardant of this invention, the compound shown by following formula (1), (2) can also be used as a carbodiimide group containing compound. When these compounds are used, a carbodiimide group-containing organic layer can be efficiently formed on the surface of the inorganic hydroxide, which is particularly preferable.
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -NCO] l (1)
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -A-Z- (X 2) 3] l (2)

In the above formulas (1) and (2), R ¹ represents a residue from an isocyanate compound. The residue from an isocyanate compound is a partial structure obtained by removing an isocyanate group from an organic isocyanate compound that remains in the carbodiimide compound when a (poly) carbodiimide compound is produced from the isocyanate compound.
X ¹ and X ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may contain an unsaturated structure, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, Or a C1-C20 alkoxy group is represented. When there are a plurality of X ¹ , they may be the same or different from each other, and the plurality of X ² may be the same or different from each other.

The halogen atom may be any of fluorine, chlorine, bromine and iodine atoms.
The alkyl group having 1 to 20 carbon atoms which may contain an unsaturated structure may have any of a linear, branched or cyclic structure, such as a methyl group, an ethyl group, or an n-propyl group. , N-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl and the like.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a biphenyl group.
A benzyl group etc. are mentioned as a C7-C20 aralkyl group.
As a C1-C20 alkoxy group, a methoxy group, an ethoxy group, n-butoxy group, t-butoxy group, a phenoxy group etc. are mentioned, for example. In addition, the alkyl group in the alkoxy group may have any structure of linear, branched or cyclic.

A represents a divalent or higher-valent organic group containing a bond derived from an isocyanate group.
The bond derived from an isocyanate group includes a bond formed by a reaction between an isocyanate group and a functional group capable of reacting with the isocyanate group.
The functional group that can react with the isocyanate group is not particularly limited, and examples thereof include a hydroxyl group, a primary or secondary amino group, a carboxyl group, and a thiol group.
Examples of bonds formed by the reaction of these functional groups with isocyanate groups include urethane bonds, thiourethane bonds, urea bonds, amide bonds, carbodiimide bonds, allophanate bonds, burette bonds, acylurea bonds, uretonimine bonds, and isocyanate dimerization. Bond, isocyanate trimerization bond and the like. Among these, at least one selected from a urea bond, a urethane bond, a thiourethane bond, and an amide bond is preferable because it can easily react at a relatively low temperature to form a bond.
A may further include a linking group between the bond derived from the isocyanate group and Z. Such a linking group is not particularly limited. For example, — (CH ₂ ) _k —, — (CH ₂ ) _k —NH— (CH ₂ ) _k —, —CO—NH— (CH ₂ ) _k- (in the above, k represents an integer of 1 to 20), -CO-O-, -O- and the like.

M in the above (X ¹ ) _m is an integer of 1 to 3, but preferably m = 3 (particularly in the case of the compound of formula (1)).
When a plurality of X ¹ are present, considering the reactivity of the compounds represented by formulas (1) and (2) with the surface of the inorganic hydroxide, at least one of them preferably has 1 to 20 carbon atoms, preferably Are preferably 1 to 5 alkoxy groups, and most preferably all are 1 to 5 alkoxy groups.
On the other hand, as X ^2, for the same reason, at least one of them is preferably a C 1-20, preferably 1-5 alkoxy group, and all are C 1-5 alkoxy groups. It is best to be.
In addition, as a C1-C5 alkoxy group, a methoxy group and an ethoxy group are suitable.
m and l are integers of 1 to 3 and a number satisfying m + 1 = 4, and corresponding to m, l is preferably 1 (particularly in the case of formula (1)).

Z is independently a silicon or titanium atom. Here, in the above formula (1), (X) _m -Z- is at least one of (X ¹ ) _m -Z- and -Z- (X ² ) _{3 in} the above formula (2). It is preferably a site that can act as a coupling agent.
Considering this point, it is preferable that Z in the formula (1) and two Zs in the formula (2) are silicon atoms. In this case, the above formulas (1) and (2) are represented by the following formulas (1 ′) and (2 ′), respectively.
_{^{(X 1) m -Si- [A-}} (R 1 -N = C = N) n -R 1 -NCO] l (1 ')
_{^{(X 1) m -Si- [A-}} (R 1 -N = C = N) n -R 1 -A-Si- (X 2) 3] l (2 ')
(Wherein X ¹ , X ² , A, R ¹ , l, m and n are the same as above)

The compound represented by the formula (1) or (2) preferably has a weight average molecular weight of 300 to 100,000, more preferably 500 to 50,000, still more preferably 600 to 40,000, and most preferably 1, 000 to 20,000. If the weight average molecular weight is more than 100,000, the steric hindrance increases, so that the surface treatment effect of efficiently surface-modifying the inorganic hydroxide may be impaired.
The above n is an integer of 1 to 100, but as described above, 2 to 80 is more preferable in consideration that the steric hindrance increases and the surface treatment effect decreases as the weight average molecular weight increases. .

The carbodiimide group-containing compound represented by the above formula (1) or (2) is, for example, a functional group or bond capable of reacting with an isocyanate group of the carbodiimide compound at any stage of the compound production represented by (I). It can be obtained by reacting a coupling agent containing a silicon or titanium atom having a group.
The functional group or bonding group having reactivity with the isocyanate group in the coupling agent is not limited as long as it is a group that can react with the isocyanate group. Specific examples thereof include a hydroxyl group, an amino group (preferably primary or secondary), a carboxyl group, a thiol group, an isocyanate group, an epoxy group, a urethane bond, a urea bond, an amide bond, and an acid anhydride group. Among them, an amino group (preferably primary or secondary), a thiol group, an isocyanate group, and an epoxy group that are widely available are preferable.

Specific examples of the silane coupling agent include the following.
Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, and γ-aminopropyl. Methyldiethoxylane, γ-aminopropyldimethylethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxy Silane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethyldiethoxysilane, etc. Can be mentioned.

Examples of the silane coupling agent having a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyldimethylethoxysilane, (mercaptomethyl) methyldiethoxysilane, and 3-mercaptopropylmethyl. Examples include dimethoxysilane.
Examples of the coupling agent having an isocyanate group include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxylane, γ-isocyanatopropyldimethylmethoxysilane, and γ-isocyanatopropylmethyl. Examples thereof include diethoxysilane and γ-isocyanatopropyldimethylethoxysilane.

  Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxylane, and γ-glycidoxypropyl. Dimethylmethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxy Propylethyldiethoxysilane, γ-glycidoxypropyldiethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3 , 4-Epo Cycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethylethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxypropylmethyldimethoxysilane, 3-epoxypropyldi Tylmethoxysilane, 3-epoxypropylmethyldiethoxysilane, 3-epoxypropyldimethylethoxysilane, 3-epoxypropylethyldimethoxysilane, 3-epoxypropyldiethylmethoxysilane, 3-epoxypropylethyldiethoxysilane, 3-epoxypropyl Diethylethoxysilane, 4-epoxybutyryltrimethoxysilane, 6-epoxyhexyltrimethoxysilane, 8-epoxyoctyltrimethoxysilane, 4-epoxybutyryltriethoxysilane, 6-epoxyhexyltriethoxysilane, 8-epoxyoctyltriethoxy Silane etc. are mentioned.

On the other hand, specific examples of titanate coupling agents include titanium acylate, titanium acylate polymer, titanium phosphate polymer, titanium alcoholate, and the like.
The coupling agents exemplified above may be used alone or in combination of two or more.

  Among these coupling agents, γ-glycidoxypropyltrimethoxysilane and γ-glycid are preferred because they are excellent in water resistance, adhesion to inorganic hydroxide, coating film hardness, stain resistance, pot life and the like. Xylpropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane Γ-isocyanatopropyltriethoxysilane is preferred .

The reaction temperature between the isocyanate group and the coupling agent is generally about −50 to 200 ° C., but considering the suppression of the reaction between the carbodiimide group and the coupling agent, −30 to 100 ° C., particularly A relatively low temperature of about −10 to 50 ° C. is suitable.
In addition, as long as the performance of a carbodiimide group containing organic layer is not impaired, you may make a carbodiimide group and a coupling agent react.

  The carbodiimide compounds represented by the formulas (I), (1), and (2) described above preferably have an average number of carbodiimide groups in one molecule of about 1 to 100, more preferably 2 to 80. It is a piece. When the number of carbodiimide groups is less than 1, the characteristics as a carbodiimide compound may not be sufficiently exhibited, and when it exceeds 100, synthesis is possible, but the polymer may be polymerized and handling may be difficult.

  Furthermore, as a carbodiimide group containing compound in the flame retardant of this invention, it has at least 1 sort (s) of the repeating unit shown by following formula (3) and formula (4), and the repeating unit shown by Formula (5) as needed. (Co) polymers can also be used. By setting it as such a (co) polymer, there exists an advantage that a carbodiimide group can be efficiently contained in various polymers.

〔式中、Ｒ²は、イソシアネート基と反応し得る基および重合性官能基を有するモノマー由来の部分構造を表し、Ｂ¹は、イソシアネート基と上記イソシアネート基と反応し得る基とが反応して生成した結合基を表す。Ｒ³は、カルボジイミド基と反応し得る基および重合性官能基を有するモノマー由来の部分構造を表し、Ｂ²は、カルボジイミド基と上記カルボジイミド基と反応し得る基とが反応して生成した結合基を表す。Ｒ⁴は、重合性官能基を有し、イソシアネート基およびカルボジイミド基と反応し得る官能基を有しないモノマー由来の部分構造を表す。Ｒ¹およびｎは、上記と同じ。〕

[Wherein R ² represents a partial structure derived from a monomer having a group capable of reacting with an isocyanate group and a polymerizable functional group, and B ¹ represents a reaction between the isocyanate group and a group capable of reacting with the isocyanate group. Represents the generated linking group. R ³ represents a partial structure derived from a monomer having a group capable of reacting with a carbodiimide group and a polymerizable functional group, and B ² is a bonding group formed by reacting a carbodiimide group with a group capable of reacting with the carbodiimide group. Represents. R ⁴ represents a partial structure derived from a monomer having a polymerizable functional group and having no functional group capable of reacting with an isocyanate group and a carbodiimide group. R ¹ and n are the same as above. ]

R ² is a partial structure formed by a monomer having a group capable of reacting with an isocyanate group and a polymerizable functional group reacting with the isocyanate group and further polymerizing with the polymerizable functional group, and the main chain of the (co) polymer Configure. Examples of the functional group capable of reacting with an isocyanate group include a hydroxyl group, a primary or secondary amino group, a carboxyl group, and a thiol group.
R ³ is a partial structure formed by a monomer having a group capable of reacting with a carbodiimide group and a polymerizable functional group reacting with the carbodiimide group and further polymerizing with the polymerizable functional group, and the main chain of the (co) polymer Configure. Examples of the functional group capable of reacting with the carbodiimide group include a hydroxyl group, an amino group (preferably primary or secondary), a carboxyl group, a thiol group, an isocyanate group, an epoxy group, a urethane bond, a urea bond, an amide bond, and an acid anhydride. Thing etc. are mentioned.
The polymerizable functional groups of R ² , R ³ and R ⁴ are not particularly limited, but are preferably a polymerizable double bond in view of the polymerizability and the convenience of the reaction operation.

  Specific examples of the monomer having a group capable of reacting with an isocyanate group or a carbodiimide group and a polymerizable functional group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxylpropyl acrylate, 2-hydroxylpropyl methacrylate, penta Erythritol triacrylate, pentaerythritol trimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, allylamine, N-methylallylamine, N-ethyl-2-methylallylamine, Diallylamine, allylcyclohexylamine, butadiene monoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, allylglycol Zyl ether, 2-allyl phenol, 2-allyloxyethanol, pentaerythritol triallyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-sulfoethyl methacrylate, polyethylene glycol monoarylate, 2- Examples include hydroxy-1,3-dimetachloroxypropane and polypropylene glycol monoacrylate. These can be used alone or in combination of two or more.

R ⁴ is a partial structure formed by polymerization of a monomer having a polymerizable functional group and not having a functional group capable of reacting with an isocyanate group and a carbodiimide group with the polymerizable functional group. Construct a chain. In addition, this monomer is an arbitrary component used as needed.
Specific examples of the monomer having this polymerizable functional group and not having a functional group capable of reacting with an isocyanate group and a carbodiimide group include olefins such as ethylene and propylene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, Styrenes such as pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-dichloro styrene, acrylic acid Methyl, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid pro Hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate , Ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, (meth) Vinyl ethers such as acrylonitrile, (meth) acrylic acid derivatives such as (meth) acrylate and methyl (meth) acrylate, vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether , Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, vinyl fluoride, fluorine Compounds having a fluorinated alkyl group such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate, ethyl bromide, (S) -3-bromo-3-methylhexane, chloro Examples thereof include halogenated organic compounds such as methane, and these can be used alone or in combination of two or more. Among these, styrenes and (meth) acrylic acid derivatives are preferable in consideration of versatility and reactivity, and styrene and methyl methacrylate are particularly preferable.

A carbodiimide group contained in one molecule of a (co) polymer having at least one repeating unit represented by the above formulas (3) and (4) and, if necessary, a repeating unit represented by the formula (5). The number of is preferably about 1 to 100 on average, more preferably 2 to 80. When the number of carbodiimide groups is less than 1, the characteristics as a carbodiimide group-containing compound may not be sufficiently exhibited, and when it exceeds 100, synthesis is possible, but polymerization makes it difficult to handle There is.
The weight average molecular weight of the (co) polymer is preferably 1,000 to 1,000,000, more preferably 2,500 to 950,000, still more preferably 5,000 to 500,000, and most preferably 10,000 to 300,000.

In addition, the various carbodiimide group-containing compounds described above can be used as a flame retardant by changing the composition, adjusting the molecular weight, or changing the end-capping segment (in the case of formulas (I), (1), (3), (4)). It is possible to control the cohesion and the dispersibility with respect to the organic resin. Moreover, although all the isocyanate groups in a carbodiimide group containing compound may be sealed, you may leave an isocyanate group arbitrarily to one terminal or both terminals.
Examples of general compounds that can be used as a sealant, that is, react with an isocyanate group are shown in the following (a) to (j).

(A) Hydroxyl (—OH) group-containing compound (i) 1 such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, tert-butanol, n-octanol, n-dodecyl alcohol, etc. (Ii) ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neo Saturated or unsaturated glycols such as pentyl glycol, pentanediol, hexanediol, octanediol, 1,4-butenediol, diethylene glycol, triethylene glycol, dipropylene glycol; (iii) methyl cellosolve, ethyl cellosolve, Cellosolves such as butyl cellosolve; (iv) (meth) acrylic such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (V) Polyalkylene glycol (meth) acrylic compounds such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; (vi) Various hydroxys such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether Alkyl vinyl ethers; (vii) various allyl compounds such as allyl alcohol and 2-hydroxyethyl allyl ether; (viii) n-butyl glycidyl ether, 2-ethylhexyl glycy Alkyl glycidyl ethers such as ether; (ix) polyethylene glycol, hydroxyl group-containing polymers such as polypropylene glycol. These may be used alone or in combination of two or more.

(B) mercapto group-containing compound (i) methanethiol, ethanethiol, n- or iso-propanethiol, n- or iso-butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, Aliphatic alkyl monofunctional thiols such as cyclohexanethiol; (ii) 1,4-dithian-2-thiol, 2- (1-mercaptomethyl) -1,4-dithiane, 2- (1-mercaptoethyl) -1 , 4-dithiane, 2- (1-mercaptopropyl) -1,4-dithiane, 2- (mercaptobutyl) -1,4-dithiane, tetrahydrothiophene-2-thiol, tetrahydrothiophene-3-thiol, pyrrolidine-2 -Thiol, pyrrolidine-3-thiol, tetrahydride (Iii) 2-mercaptoethanol, 3-mercaptoethanol having a heterocyclic ring such as lofuran-2-thiol, tetrahydrofuran-3-thiol, piperidine-2-thiol, piperidine-3-thiol, piperidine-4-thiol; Aliphatic thiols having a hydroxy group such as mercaptopropanol and thioglycerol; (iv) 2-mercaptoethyl (meth) acrylate, 2-mercapto-1-carboxyethyl (meth) acrylate, N- (2-mercaptoethyl) ) Acrylamide, N- (2-mercapto-1-carboxyethyl) acrylamide, N- (2-mercaptoethyl) methacrylamide, N- (4-mercaptophenyl) acrylamide, N- (7-mercaptonaphthyl) acrylamide, maleic acid Mono 2-mercapto Compounds having an unsaturated double bond such as tilamide; (v) 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiol Propionate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris (2-mercaptoethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate (Vi) 1,2-benzenedithiol, 1,4-benzenedithiol, 4-methyl-1,2-benzenedithiol, 4-butyl-1,2-benzenedithiol, 4-chloro-1 And aromatic dithiols such as 2-benzenedithiol; (vii) polymers containing mercapto groups such as modified polyvinyl alcohol having mercapto groups. These may be used alone or in combination of two or more.

(C) Amino group-containing compound (i) Ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, monoethanolamine, n-propanolamine, isopropanolamine, aniline, cyclohexylamine, n-butylamine, n-pentylamine N-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-penta Decylamine, cyclohexylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, diethylamine, diethanolamine, dibutylamine, din-propanolamine, diisopropano Aliphatic or aromatic amine-containing compounds such as dimethylamine, N-methylethanolamine, N-ethylethanolamine; (ii) dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, diacrylate and diethylamine Alkylaminoacrylates such as adducts of trimethylolpropane triacrylate and diethylamine; (iii) (meth) acrylamide, α-ethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (Meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl- -Styrenesulfonamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethylene] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- (N, N- (Dimethylamino) styrene, 4- (N, N-diethylamino) styrene, 4-vinylpyridine, 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether, 6-di And alkylaminoalkyl vinyl ethers such as methylaminohexyl vinyl ether; (iv) polymers containing amino groups. These may be used alone or in combination of two or more.

(D) Carboxyl group-containing compound (i) Fatty acids such as formic acid, acetic acid, propionic acid, isovaleric acid, hexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, linolenic acid Or saturated aliphatic monocarboxylic acids such as higher fats; (ii) saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid; (iii) 2-acryloyloxyethyl succinic acid, 3-acryloyloxypropyl phthalic acid, etc. (Iv) carbocyclic carboxylic acids such as benzoic acid, toluic acid and salicylic acid; (v) heterocyclic carboxylic acids such as furan carboxylic acid, thiophene carboxylic acid and pyridine carboxylic acid; (vi) Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid Unsaturated mono- or dicarboxylic acids such as monobutyl itaconate, monobutyl maleate or unsaturated dibasic acids; (vii) acid anhydrides derived from carboxylic acids such as acetic anhydride, succinic anhydride, phthalic anhydride; (viii) Examples thereof include polymer carboxylic acids such as polyacrylic acid and polymethacrylic acid. These may be used alone or in combination of two or more.

(E) Isocyanate group-containing compound (i) Cyclohexyl isocyanate, n-decyl isocyanate, n-undecyl isocyanate, n-dodecyl isocyanate, n-tridecyl isocyanate, n-tetradecyl isocyanate, n-pentadecyl isocyanate, n-hexa Isocyanate compounds such as decyl isocyanate, n-heptadecyl isocyanate, n-octadecyl isocyanate, n-eicosyl isocyanate, phenyl isocyanate, naphthyl isocyanate; (ii) isocyanate compounds having two or more isocyanate groups as used in carbodiimide compounds Etc.

(F) Epoxy-containing compound (i) Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether Glycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; (ii) polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol di Glycidyl ethers of polyalkylene glycols such as glycidyl ether; (i (ii) Polyglycidylated product of polyester resin; (iv) Polyglycidylated product of polyamide resin; (v) Bisphenol A epoxy resin; (vi) Phenol novolac epoxy resin; (vii) Epoxy urethane resin; (viii) ) Glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate And epoxy group-containing monomers such as di (β-methyl) glycidyl fumarate.

  In addition, a commercial item can also be used for an epoxy compound, for example, "Denacol" series, "Denacol EX-611", -612, -614, -614B, -622, -512 by Nagase Chemtech Co., Ltd. -521, -411, -421, -313, -314, -321, -201, -211, -212, -252, -810, -811, -850, -851, -821, -830,- 832, -841, -861, -911, -941, -920, -931, -721, -111, -212L, -214L, -216L, -321L, -850L, -1310, -1410, -1610, Epoxy compounds such as −610U may be used.

Further, from the viewpoint of reducing environmental burden, a water-soluble carbodiimide compound may be used.
Examples of the water-soluble carbodiimide compound include those having a hydrophilic segment at the end of the carbodiimide compound. As the hydrophilic segment, at least one of the following residues may be used.

(G) Residue of alkyl sulfonate having at least one reactive hydroxyl group represented by formula (6) R ⁶ —SO ₃ —R ⁵ —OH (6)
(In the formula, R ⁵ represents an alkylene group of 1 to 10, and R ⁶ represents an alkali metal.)
Examples of the alkyl sulfonate include sodium hydroxyethane sulfonate and sodium hydroxypropane sulfonate, and among them, sodium hydroxypropane sulfonate is preferable.

(H) Quaternary salt of residue of dialkylamino alcohol represented by formula (7) (R ⁷ ) ₂ —N—R ⁸ —OH (7)
(In the formula, R ⁷ represents a lower alkyl group having 1 to 4 carbon atoms, and R ⁸ represents an alkylene group or oxyalkylene group having 1 to 10 carbon atoms.)
Examples of the dialkylamino alcohol include 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 3-diethylamino-2-propanol, and 5-diethylamino-2- Examples include propanol and 2- (di-n-butylamino) ethanol. Among them, 2-dimethylaminoethanol is preferable.

(I) Amine residue represented by formula (8) (R ⁷ ) ₂ —NR′—R ⁸ —OH (8)
(Wherein R ⁷ and R ⁸ are the same as those in the chemical formula (7), and R ′ represents a group derived from a quaternizing agent)
Examples of the quaternizing agent include dimethyl sulfate and methyl p-toluenesulfonate.

(J) Residue of poly (alkylene oxide) having at least one reactive hydroxyl group represented by the formula (9) and end-capped with an alkoxy group R ⁹ — (O—CHR ¹⁰ —CH ₂ ) _o — OH (9)
(In the formula, R ⁹ represents a lower alkyl group having 1 to 4 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, and o is an integer of 2 to 30.)
Examples of the poly (alkylene oxide) include poly (ethylene oxide) monomethyl ether, poly (ethylene oxide) monoethyl ether, poly (ethylene oxide / propylene oxide) monomethyl ether, poly (ethylene oxide / propylene oxide) monoethyl ether, and the like. Among them, poly (ethylene oxide) monomethyl ether is preferable.

The compound which reacts with the isocyanate group demonstrated above may be used independently, and may use 2 or more types together.
In addition, the compound which reacts with an isocyanate group is not limited to the representative compounds described in the above (a) to (j), but is a compound having a functional group or a linking group which reacts with other isocyanate groups (for example, acid anhydrides). Or the like) may be used.

In particular, in electronic material applications, a composition obtained by adding a flame retardant to an organic resin is required to have high dispersibility in an organic resin and an organic solvent in consideration of the properties and moldability of the flame retardant, and at the same time etching treatment. In order to prevent adverse effects on the electrical properties such as acid resistance, dielectric constant, electrical conductivity, migration resistance, etc. necessary for the above, water resistance and the like are very important. For this reason, the end-capping segment is preferably lipophilic rather than hydrophilic, and the resulting compound is preferably not water-soluble.
Examples of the end-capping agent for obtaining the above compound include hydroxyl group-containing compounds such as methanol, ethanol, propanol, dodecyl alcohol, octanol; oxalic acid, salicylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, Carboxyl group-containing compounds such as oleic acid, linoleic acid and linolenic acid; mercapto group-containing compounds such as methanethiol, ethanethiol, propanethiol and ammonia; amino such as methylamine, ethylamine, dibutylamine, cyclohexylamine and n-dodecylamine Group-containing compounds are preferred, but considering dispersibility in resins, production costs, etc., dodecyl alcohol, octanol; dibutylamine, cyclohexylamine; lauric acid, myristic acid, palmitic acid, Phosphoric acid, arachidic acid, carboxyl group-containing compounds such as oleic acid are preferred.

The flame retardant of the present invention (inorganic hydroxide having a carbodiimide group-containing organic layer, the same shall apply hereinafter) uses tetrahydrofuran (hereinafter referred to as THF) as a dispersion medium from the viewpoint of dispersibility of the flame retardant in an organic solvent or an organic resin. When used, it is preferable to satisfy the following formula.
The relationship between the standard deviation (A ₁ ) of the particle size distribution of the surface untreated inorganic hydroxide and the standard deviation (A ₂ ) of the particle size distribution of the inorganic hydroxide having the carbodiimide group-containing organic layer is (A ₂ ) / (A ₁ ) ≦ 1.0.

Similarly, from the viewpoint of dispersibility of the flame retardant in an organic solvent or an organic resin, the flame retardant of the present invention preferably satisfies the following formula when THF is used as a dispersion medium.
The relationship between the volume average particle diameter (M ₁ ) of the surface untreated inorganic hydroxide and the volume average particle diameter (M ₂ ) of the inorganic hydroxide provided with the carbodiimide group-containing organic layer is (M ₂ ) / ( M ₁ ) ≦ 1.0.

Furthermore, from the viewpoint of the lipophilicity of the flame retardant, the dispersibility of the flame retardant in the organic resin during molding, the physical properties after molding, etc., the flame retardant of the present invention is as follows when water at pH 7 is used as the dispersion medium. It is preferable to satisfy the formula.
The relationship between the standard deviation (A ₃ ) of the particle size distribution of the surface untreated inorganic hydroxide and the standard deviation (A ₄ ) of the particle size distribution of the inorganic hydroxide provided with the carbodiimide group-containing organic layer is (A ₄ ) / (A ₃ )> 1.0.
More preferably, considering dispersibility of the organic resin during molding, physical properties after molding, etc., (A ₄ ) / (A ₃ )> 1.5, and the optimum is (A ₄ ) / (A ₃ )> 1.8.

Similarly, from the viewpoint of lipophilicity of the filler, dispersibility to the organic resin during molding, physical properties after molding, and the like, the flame retardant of the present invention, when water at pH 7 is used as a dispersion medium, It is preferable to satisfy the following formula.
The volume average particle diameter (M ₃ ) of the surface untreated inorganic hydroxide and the volume average particle diameter (M ₄ ) of the inorganic hydroxide provided with the carbodiimide group-containing organic layer are (M ₄ ) / (M ₃ )> 1.0
More preferably, considering the dispersibility of the organic resin during molding, physical properties after molding, etc., (M ₄ ) / (M ₃ )> 1.2, and the optimum is (M ₄ ) / (M ₃ )> 1.5.

The above volume average particle diameter is a value measured by a particle size analyzer of a laser diffraction / scattering type or a dynamic light scattering type. More specifically, an inorganic substance is added to THF or pH 7 water and dispersed. It is the value measured using the prepared sample of the density | concentration measurable with the particle size analyzer to be used.
Here, the standard deviation is a measure of the distribution width of the measured particle size distribution, and is a value calculated by the following equation.
Standard deviation = (d84% −d16%) / 2
d84%: Volume average particle diameter at the point where the cumulative curve is 84% (micrometer)
d16%: Volume average particle diameter at the point where the cumulative curve is 16% (micrometer)
“Surface untreated inorganic hydroxide” means an inorganic hydroxide not only having no carbodiimide group-containing organic layer but also having no other surface modification (not treated with a surface treatment agent). To do. Moreover, each inorganic hydroxide which comprises the inorganic hydroxide provided with the surface untreated inorganic hydroxide and the carbodiimide group containing organic layer is the same.

Hereinafter, the manufacturing method of the flame retardant of this invention is demonstrated.
The carbodiimide group-containing organic layer in the present invention may be either a layer composed only of a carbodiimide group-containing compound or a layer formed by adding a carbodiimide group to a layer composed of an organic compound not containing a carbodiimide group.
Here, "the layer which provided the carbodiimide group with respect to the layer which consists of an organic compound which does not contain a carbodiimide group" is a layer formed by grafting a carbodiimide group-containing compound to an organic layer not containing a carbodiimide group, Alternatively, it means a copolymer layer of an organic substance not containing a carbodiimide group and a carbodiimide group-containing compound.

In the present invention, when the organic layer comprising the carbodiimide group-containing compound is formed on the surface of the inorganic hydroxide, the functional group, ionic component or surface charge present on the inorganic hydroxide itself, and the carbodiimide group directly or indirectly What is necessary is just to couple | bond a containing compound with chemical bonds, such as a covalent bond, a hydrogen bond, a coordination bond, and an ionic bond.
The reaction between the inorganic hydroxide and the carbodiimide group-containing compound may be appropriately selected from known methods depending on the type of bond. For example, a compound represented by the above formulas (I), (1), (2) and a (co) polymer containing repeating units of the formulas (3), (4) are prepared by polymerization, and these are inorganic. Examples thereof include a method of chemically bonding to the hydroxide surface. Examples of the chemical bond between the inorganic hydroxide surface and the carbodiimide group-containing compound include a covalent bond, a hydrogen bond, and a coordination bond.
In addition, as a coupling | bonding reaction of an inorganic hydroxide and a carbodiimide group containing compound, a dehydration reaction, a substitution reaction, an addition reaction, an adsorption reaction, a condensation reaction etc. can be used, for example.
In particular, a covalent bond is preferable because an inorganic substance and an organic component form a strong bond.

When the organic layer is formed based on the functional group of the inorganic hydroxide itself, the surface of the inorganic hydroxide may be modified with a compound having a reactive functional group in advance. By thus surface modification, the bond between the inorganic hydroxide and the carbodiimide group-containing organic layer can be further strengthened.
Examples of the reactive functional group include a hydroxyl group, an amino group (preferably primary or secondary), a carboxyl group, a thiol group, an isocyanate group, an epoxy group, a urethane bond, a urea bond, an amide bond, and an acid anhydride). And polymerizable double bonds.

As a method for modifying the inorganic hydroxide with a compound having these reactive functional groups, various known methods can be adopted, but a method of treating with a surface treatment agent according to the functional group to be introduced is simple.
Examples of the surface treatment agent include unsaturated fatty acids such as oleic acid, unsaturated fatty acid metal salts such as sodium oleate, calcium oleate, and potassium oleate, unsaturated fatty acid esters, unsaturated fatty acid ethers, and surfactants. , Vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyl Examples include, but are not limited to, silane coupling agents such as trimethoxysilane, titanate coupling agents such as titanium acylate and titanium alcoholate.
In addition, the carbodiimide group-containing compound represented by the formulas (1) and (2) may have the same reactivity as the silane coupling agent and the titanate coupling agent. Even without surface treatment, there is an advantage that a carbodiimide group-containing organic layer can be efficiently formed on the surface of the inorganic hydroxide.

As another method for forming the organic layer comprising the carbodiimide group-containing compound on the surface of the inorganic hydroxide, there is a method in which a polymerization reaction is performed on the surface of the inorganic hydroxide to form a (co) polymer layer. Although the specific method is not specifically limited, For example, the following is mentioned.
(A) Inorganic hydroxylation of (co) polymerization of a raw material monomer (and a monomer giving a repeating unit of formula (5) if necessary) which gives a repeating unit of formula (3) and / or (4) containing a carbodiimide group A method for forming a carbodiimide group-containing organic layer by chemically bonding the (co) polymer to the surface of the inorganic hydroxide and extending the (co) polymer chain.
(B) (co) polymerization of a monomer not containing a carbodiimide group is performed on the surface of the inorganic hydroxide to chemically bond the (co) polymer and the inorganic hydroxide, and then the (co) heavy By reacting the group capable of reacting with the isocyanate group or carbodiimide group of the coalescence with the isocyanate group or carbodiimide group of the carbodiimide group-containing organic substance, a carbodiimide group-containing organic layer containing the structural units of formulas (3) and (4) is obtained. Method.

In the case of (a), first, a group that can react with an isocyanate group or a carbodiimide group, and a monomer having a polymerizable functional group are reacted with, for example, a carbodiimide group-containing compound of the formula (I) to form the formula (3) And / or raw material monomers giving the repeating units of (4) are prepared. Next, this raw material monomer (and the raw material monomer which gives the repeating unit of the formula (5) if necessary) is (co) polymerized on the surface of the inorganic hydroxide, and this (co) polymer is converted to inorganic hydroxide. A carbodiimide group-containing organic layer is formed by chemically bonding to the surface of the product and extending the carbodiimide group-containing compound chain (generally called grafting from).
In the case of (b), first, a group capable of reacting with an isocyanate group or a carbodiimide group and a monomer having a polymerizable functional group are (co) polymerized on the surface of the inorganic hydroxide and chemically bonded to the surface of the inorganic hydroxide. At the same time, the polymer chain is extended to form an organic layer containing no carbodiimide group. Next, a carbodiimide group-containing organic layer is formed by reacting a group capable of reacting with the isocyanate group or carbodiimide group of the organic layer with, for example, a carbodiimide compound of the formula (I) (generally grafting from Called the method).

Examples of the (co) polymerization method include addition polymerization, polycondensation, hydrogen transfer polymerization, and addition condensation.
Examples of the addition polymerization include radical polymerization, ionic polymerization, oxidation anion polymerization, ring-opening polymerization, and the like. Examples of the polycondensation include elimination polymerization, dehydrogenation polymerization, denitrogenation polymerization, and the like. Examples include polyaddition, polyaddition, isomerization polymerization, and transfer polymerization.
In particular, radical polymerization is preferable because it is a simple and economical method for producing a polymer and is frequently used for industrial synthesis of various polymers. Among them, the living radical polymerization is not yet used for general purposes or industrially, but is useful in that the molecular weight and molecular weight distribution of the polymer and the graft density can be easily controlled.

The polymerization conditions are not particularly limited, and various known conditions may be used according to the monomers used.
For example, in the case of grafting by performing radical polymerization on the surface of an inorganic hydroxide, it reacts with 0.1 mol of a reactive functional group present or introduced on the inorganic hydroxide. The amount of the monomer having a functional group to be obtained is 1 to 300 mol, and the amount of the polymerization initiator used is usually 0.005 to 30 mol. Moreover, superposition | polymerization temperature is -20-1000 degreeC normally, and superposition | polymerization time is 0.2 to 72 hours normally.
In carrying out the polymerization, various additives such as a dispersant, a stabilizer, and an emulsifier (surfactant) can be added to the polymerization reaction system as necessary.

  As a polymerization initiator used for radical polymerization, a known radical polymerization initiator can be used. Typical examples include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobismethylbutyronitrile. And azo compounds such as azobisisovaleronitrile, but are not limited thereto. These may be used alone or in combination of two or more.

The solvent used for the polymerization is not particularly limited, and a general solvent conventionally used in polymer synthesis can be used.
Specific examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2- Methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane, methylcyclohexane, ethylcyclohexane , P-menthane, dicyclohexyl, benzene, toluene, xylene, ethylbenzene, anisole (methoxybenzene) and other aliphatic or aromatic hydrocarbons; carbon tetrachloride, trichloroethylene, chlorobenzene, te Halogenated hydrocarbons such as Raburomuetan; ethyl ether, dimethyl ether, trioxane, tetrahydrofuran and the like; methylal, although acetals such as diethyl acetal, and the like, but is not limited thereto. These may be used alone or in combination of two or more.
In the present invention, an ionic liquid can also be used as a reaction solvent. By using ionic liquids, production time can be shortened, and the amount of organic solvent used can be reduced to zero or extremely low. Moreover, ionic liquids can be reused, so they are environmentally adaptable. It can also increase safety. Furthermore, if the polymerization reaction described above is performed in an ionic liquid, the thickness of the carbodiimide group-containing organic layer can be further improved, and a flame retardant superior in dispersibility in an organic resin can be obtained.
The ionic liquid is a general term for liquid salts, in particular, salts that become liquid at around room temperature, and is a solvent composed only of ions.

The ionic liquid in the present invention is not particularly limited, but the cation constituting the ionic liquid is preferably at least one selected from an ammonium cation, an imidazolium cation and a pyridinium cation. It is more preferable that
The imidazolium cation is not particularly limited, and examples thereof include a dialkyl imidazolium cation and a trialkyl imidazolium cation. Specific examples include 1-ethyl-3-methylimidazolium ion, 1-butyl-3- Methyl imidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl-2,3- Examples include dimethyl imidazolium ion.
The pyridinium cation is not particularly limited, and examples thereof include N-propylpyridinium ion, N-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-butyl-2,4-dimethylpyridinium ion, and the like. Is mentioned.

Although it does not specifically limit as an ammonium cation, It is preferable that an aliphatic or alicyclic quaternary ammonium ion is used as a cation component.
These aliphatic and alicyclic quaternary ammonium ions are not particularly limited, but are trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, diethylmethyl (2-methoxyethyl) ammonium, diethylmethyl. Examples include various quaternary alkyl ammonium ions such as (2-methoxyethyl) ammonium, N-butyl-N-methylpyrrolidinium ion, N- (2-methoxyethyl) -N-methylpyrrolidinium ion, and the like.

The anion constituting the ionic liquid is not particularly limited, and examples thereof include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , AlCl ₄ ⁻ , HSO ₄ ⁻ , ClO ₄ ⁻ , and CH _3. Anions such as SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , Cl ⁻ , Br ⁻ and I ⁻ can be used.
Suitable ionic liquids include, for example, diethylmethyl (2-methoxyethyl) ammonium bis (trifluoromethanesulfonimide) salt, diethylmethyl (2-methoxyethyl) ammonium (tetrafluoroborate) salt, N- (2-methoxyethyl) ) -N-methylpyrrolidinium bistrifluoromethanesulfonylimide salt and the like, but not limited thereto.

In the present invention, the ionic liquid may be used alone or in combination with various conventionally used solvents such as those exemplified for the polymerization reaction solvent.
When mixing an ionic liquid and a conventional solvent, the mixing amount is arbitrary, but considering the ease of post-processing, environmental adaptability and safety, the concentration of the ionic liquid in the mixed solvent Is preferably 10% by mass or more, particularly preferably 50% by mass or more, and more preferably 80 to 100% by mass.

  As yet another method of forming an organic layer comprising the above carbodiimide group-containing compound on the surface of the inorganic hydroxide, the above-mentioned organic isocyanate compound is formed on the surface of the inorganic hydroxide in the presence of a catalyst that promotes carbodiimidization of the isocyanate. And a method for forming a carbodiimide group-containing organic layer, and an inorganic hydroxide surface having a group capable of reacting with an isocyanate group or a carbodiimide group and covered with an organic layer having no carbodiimide group, as described above. Examples include a method of polymerizing an organic isocyanate compound in the presence of a catalyst that promotes carbodiimidization of isocyanate to form a carbodiimide group-containing organic layer.

In the flame retardant of the present invention, the carbodiimide group-containing organic layer is preferably present at least 0.1% by mass or more based on the inorganic hydroxide. In particular, considering the dispersibility of the flame retardant in the organic resin and the electrical and mechanical properties of the obtained molded product, it is more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more. The optimum is 1.0% by mass or more.
In addition, the mass% of the carbodiimide group-containing organic layer is the organic layer in 1 cm ^{3 of the} inorganic hydroxide having an organic layer, based on the density measured by a density meter (Accubic 1330, manufactured by Shimadzu Corporation: in a helium atmosphere). It is the calculated value which calculated | required the volume of this and the volume of the inorganic hydroxide, and calculated | required from those values.

The thickness of the carbodiimide group-containing organic layer is not particularly limited, but considering the dispersibility of the flame retardant in the organic resin, and the electrical and mechanical properties of the obtained molded product, Since it depends on the type of carbodiimide resin, the surface area to be coated, etc., it cannot be generally stated, but for example at the μ level, the average is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 3 nm or more. The thickness of the organic layer is determined based on the density measured by a density meter (Accubic 1330, manufactured by Shimadzu Corporation: in a helium atmosphere), and the volume of the organic layer and the volume of the inorganic hydroxide in 1 cm ^{3 of} the flame retardant. The total surface area was calculated and calculated from these values. What is the volume and surface area at this time? It is assumed that the flame retardant is spherical.

  The organic resin constituting the inorganic-organic composite flame retardant composition of the present invention is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polystyrene resins such as polystyrene, polyvinyl chloride, Polyvinyl halide derivative resins such as polyvinylidene chloride, polyvinyl acetate derivative resins such as polyvinyl acetate, poly (meth) acrylic resins such as polymethyl methacrylate, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isobutyl ether, etc. Polyvinyl ketones such as polyvinyl ethers, polyvinyl methyl ketone, polyvinyl hexyl ketone, polymethyl isopropenyl ketone, poly N-vinyl pyrrole, poly N-vinyl carbazole, poly N-vinyl indole, poly N-vinyl pyrrolide Such as poly N-vinyl compounds, fluororesins, polyamides such as nylon-6, polyesters, polycarbonates, silicones, polyacetals, acetylcellulose, etc .; epoxy resins, phenol resins, urea resins, melamine resins And thermosetting resins such as alkyd resins and unsaturated polyester resins.

Among them, in consideration of environmental adaptability and variety of uses of the composition, polystyrene resins, polyolefin resins, poly (meth) acrylic resins, carboxylic acid vinyl ester resins such as polyvinyl acetate, epoxy resins, etc. Is preferably used.
The blending ratio of the flame retardant and the organic resin is not particularly limited, but considering the balance between various functional improvement effects and physical properties degradation by blending the flame retardant, the flame retardant (untreated inorganic hydroxylation) Standard): Organic resin = 5: 95 (mass ratio) to 90:10 (mass ratio) is preferable, more preferably 10:90 (mass ratio) to 80:20 (mass ratio), and even more preferably. Is 15:85 (mass ratio) to 85:15 (mass ratio).

Preparation of a composition should just mix a flame retardant and organic resin by arbitrary methods, and can also use the solvent in the case of mixing.
The solvent used in preparing the composition is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; Pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, Nonane, cyclopentane, methylcyclopentane, methylcyclohexane, ethylcyclohexane, p-menthane, benzene, toluene, xylene, ethylbenzene and other aliphatic or aromatic hydrocarbons; carbon tetrachloride, trichloroethylene, chlorobenzene Halogenated hydrocarbons such as tetrabromoethane; ethers such as ethyl ether, dimethyl ether, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; sulfur and nitrogen such as nitropropene, nitrobenzene, pyridine, dimethylformamide and dimethyl sulfoxide Examples thereof include organic compounds. Considering the solubility, moldability, molding efficiency, etc. of the organic resin, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, toluene, tetrahydrofuran and the like are optimal. These may be used alone or in combination of two or more.

Further, the compositions of the present invention preferably has a total surface area of the flame retardant in the composition 1g is 2000cm ² ~1000000cm ^2, more preferably 4000cm ² ~600000cm ^2, even more preferably 10000 cm ² ~ a 500000cm ^2, optimal and consider the formability and physical properties, etc. of the composition is 13000cm ² ~300000cm ^2.
Here, the total surface area indicates a theoretical value obtained by adding the surface areas of all flame retardants added to the organic resin. The surface area is based on the assumption that the flame retardant is spherical, and the particle size is a volume average particle size.
The flame retardant of the present invention is excellent in dispersibility in an organic resin and an organic solvent, and even when the organic resin is highly filled, the electrical properties, mechanical properties, heat resistance and water absorption of the resulting molded product are obtained. Therefore, the composition can be blended at a high ratio of 15% by mass or more and a total surface area of 2000 cm ² (in 1 g of the composition) or more.

  Furthermore, it is preferable that the inorganic-organic composite flame retardant composition of the present invention has a low expansion coefficient. Moreover, it is preferable that it has each characteristic (1)-(3) shown below. In the following (1) to (3), the organic resins constituting both compositions are the same. Further, the composition in the present invention is a concept including a molded product obtained by molding this composition in addition to a mixed amorphous composition obtained by simply mixing a flame retardant and an organic resin.

(1) The dielectric constant of the inorganic-organic composite flame retardant composition and the inorganic hydroxide having no organic layer instead of the flame retardant in the inorganic-organic composite flame retardant composition on the basis of the inorganic hydroxide The dielectric constant of the composition added in the same amount (untreated inorganic hydroxide added composition) is the dielectric constant of the inorganic-organic composite flame retardant composition / dielectric constant of the untreated inorganic hydroxide added composition <1. 0.0, preferably 0.99.
When the dielectric constant ratio is 1.0 or more, the effect of preventing increase in dielectric constant by the carbodiimide-containing organic layer formed on the surface of the inorganic hydroxide becomes insufficient.
The dielectric constant is a value measured at a frequency of 1 GHz using a dielectric constant measuring apparatus (4291B impedance material analyzer, manufactured by Agilent Technologies).

(2) The elastic modulus of the inorganic-organic composite flame retardant composition and the inorganic hydroxide having no organic layer in place of the flame retardant in the inorganic-organic composite flame retardant composition on the basis of the inorganic hydroxide The elastic modulus of the composition added in the same amount (untreated inorganic hydroxide added composition) is the elastic modulus of the inorganic-organic composite flame retardant composition / elastic modulus of the untreated inorganic hydroxide added composition> 1. .10, preferably 1.20.
When the elastic modulus ratio is 1.10 or less, the mechanical strength of a molded product obtained by molding the composition may be weakened. In addition, it is estimated that this reason is a result that the dispersibility of the flame retardant with respect to an organic resin becomes inadequate.
The elastic modulus is a value measured at room temperature using a thermal analysis rheology system (EXTAR600, manufactured by Seiko Instruments Inc.).

(3) Bending stress of the inorganic-organic composite flame retardant composition and an inorganic hydroxide having no organic layer instead of the flame retardant in the inorganic-organic composite flame retardant composition on the basis of inorganic hydroxide The bending stress of the composition added with the same amount (untreated inorganic hydroxide added composition) is the bending stress of the inorganic-organic composite flame retardant composition / the bending stress of the untreated inorganic hydroxide added composition> 1. .00, preferably 1.10.
When the ratio of the bending strength is 1.00 or less, the mechanical strength of a molded product obtained by molding the composition may be weakened. In addition, it is estimated that this reason is a result which arises because the dispersibility of the flame retardant with respect to an organic resin is inadequate, or the adhesiveness of a flame retardant and organic resin is low.

Although it does not specifically limit as a use of the flame retardant of this invention and an inorganic-organic composite flame retardant composition, It is suitable for the material in which various functionality is required, such as an electronic material field | area, a building material field | area, and an automotive material field | area. Can be used.
Mainly in the field of electronic materials, as printed wiring materials, large computers, automotive electronic devices, information / communication systems, built-in capacitors, mobile phones, AV equipment, OA equipment, semiconductor packages, digital broadcast receivers, base station power amplifiers It is applied to in-vehicle metal substrates (electric power steering substrates), measuring devices, network devices such as capacitors, servers, routers, etc., sealing materials such as semiconductor packages and underfills, and wire covering materials.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

[1] Synthesis of carbodiimide group-containing compound [Synthesis Example 1]
A 300 ml three-necked flask is charged with 100 g of 4,4′-dicyclomethane diisocyanate (manufactured by Bayer, hereinafter referred to as HMDI), and 1-phenyl-2-phospholene-1-oxide (hereinafter abbreviated as p-cat) as a catalyst. ) 0.5 g was added and stirred at 180 ° C. with nitrogen bubbling for 24 hours. The obtained carbodiimide compound was diluted with 35 g of toluene (manufactured by Kanto Chemical Co., Inc.), cooled to 0 ° C., and then stirred with stirring. 3-aminopropyltriethoxysilane (silane coupling agent, manufactured by Chisso Corporation) 40 g Was slowly added dropwise. After reacting at 0 ° C. under a nitrogen atmosphere for 12 hours, it was confirmed by IR spectrum that the peak of the isocyanate group of the carbodiimide compound had disappeared, and the reaction was stopped.

[Synthesis Example 2]
In a 300 ml three-necked flask, 100 g of 1,3-bis (1-isocyanato-1-methylethyl) benzene (manufactured by Takeda Pharmaceutical Co., Ltd., hereinafter abbreviated as TMXDI) is added, and p-cat 2.0 g as a catalyst. Was added and reacted at 180 ° C. under nitrogen bubbling for 12 hours. To 10.0 g of the obtained carbodiimide compound, 0.6 g of aminostyrene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.9 g of n-dodecylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were added at 0 ° C. under nitrogen. Reacted for hours.

[2] Flame retardant (inorganic hydroxide particles having a carbodiimide group-containing organic layer)
[Example 1]
In a 100 ml eggplant flask, 40.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Mg (OH) ₂ having a volume average particle diameter of 700 nm (Kisuma 5Q: surface untreated Mg (OH) ₂ , Kyowa Chemical Co., Ltd.) (Product made) 10.0 g was well dispersed. Subsequently, 0.03 g of 3-aminopropyltriethoxysilane (silane coupling agent, manufactured by Chisso Corporation) was added and stirred at 65 ° C. for 30 minutes. Thereafter, 0.5 g of 2,4-diisocyanatotoluene (manufactured by Takeda Pharmaceutical Co., Ltd., hereinafter abbreviated as TDI) and 0.02 g of p-cat as a catalyst were added and stirred at 65 ° C. for 1 hour. P-cat 0.02 g and n-dodecyl alcohol (manufactured by Kanto Chemical Co., Inc.) 0.12 g as an end-capping agent were added and reacted at 70 ° C. for about 15 hours.
After completion of the reaction, to remove carbodiimide compound that is not bound to the unreacted monomer, Mg (OH) ₂ particles, Mg (OH) ₂ particles tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as THF) Washing and suction filtration were repeated 4 times. After washing, the IR spectrum of this particle was measured with FT-IR8900 (manufactured by Shimadzu Corporation). Absorption of a carbodiimide group appeared near 2200 cm ⁻¹ , and the carbodiimide compound was chemically bonded to the surface of magnesium hydroxide. Was confirmed.
In addition, the said volume average particle diameter is the value measured with the particle size analyzer (MICROTRACHRA9320-X100, Nikkiso Co., Ltd. product).

[Example 2]
In a 100 ml eggplant flask, 40.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Mg (OH) ₂ having a volume average particle diameter of 700 nm (Kisuma 5Q: surface untreated Mg (OH) ₂ , Kyowa Chemical Co., Ltd.) (Product made) 10.0 g was well dispersed. Subsequently, 1.0 g of the compound obtained in Synthesis Example 1 was added and stirred at 65 ° C. for 15 hours. Thereafter, in Mg (OH) to remove the compound obtained in Synthesis Example 1 which is not bonded to ₂ particles Mg (OH) ₂ particles in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as THF) Washing and suction filtration were repeated twice. After washing, the IR spectrum of the particles was measured with FT-IR8900 (manufactured by Shimadzu Corporation). Absorption of a carbodiimide group appeared in the vicinity of 2200 cm ⁻¹ , so that the carbodiimide compound obtained in Synthesis Example 1 was It was confirmed that they were chemically bonded on the Mg (OH) ₂ particles. The degree of polymerization of the carbodiimide compound was 4.5.

[Example 3]
In a 100 ml three-necked flask, 10.0 g of Mg (OH) ₂ (Kisuma 5Q: surface untreated Mg (OH) ₂ , manufactured by Kyowa Chemical Co., Ltd.) having a volume average particle size of 700 nm is well dispersed in 40.0 g of cyclohexanone. To the solution, 0.12 g of trimethoxysilane (silane coupling agent, manufactured by Chisso Corporation) was added and reacted at 65 ° C. for 30 minutes. Thereafter, 7.6 g of styrene (manufactured by Kanto Chemical Co., Ltd.), 0.4 g of methacrylic acid (manufactured by Kanto Chemical Co., Ltd.), and 0.08 g of azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) as an initiator were added. The mixture was added and reacted at 70 ° C. for 15 hours.
After completion of the reaction, magnesium hydroxide particles were washed with THF and suction filtration was repeated four times in order to remove unreacted monomers and polymers not bonded to Mg (OH) ₂ particles. After washing, when the IR spectrum of the particles was measured by FT-IR8900 ((Ltd.) manufactured by Shimadzu Corporation), absorption derived from a carboxylic acid in the vicinity of 1720 cm ^-1 is absorption from the benzene ring was observed at around 700 cm ^-1 From this, it was confirmed that the copolymer of carboxylic acid and styrene was chemically bonded onto the Mg (OH) ₂ particles.

Subsequently, 0.3 g of TDI was added to a solution in which 10 g of Mg (OH) ₂ particles in which the above polymer layer was formed was well dispersed in 20 g of cyclohexanone (Daishin Chemical Industry Co., Ltd.) in a 50 ml three-necked flask, Stir at 65 ° C. for 1 hour. 0.02 g of p-cat as a post-catalyst and 0.12 g of n-dodecyl alcohol as an end-capping agent were added and reacted at 70 ° C. for 15 hours. After the reaction, in order to remove unreacted monomers, the Mg (OH) ₂ particles were washed with THF and suction filtration was repeated 4 times. When the IR spectrum of the particles was measured again after washing, absorption of a carbodiimide group newly appeared in the vicinity of 2200 cm ⁻¹ , so that the carbodiimide compound reacted with the carboxyl group in the copolymer of methacrylic acid and styrene. It was confirmed that the styrene-methacrylic acid copolymer was grafted.

[Example 4]
In a 100 ml three-necked flask, 10.0 g of Mg (OH) ₂ (Kisuma 5Q: surface untreated Mg (OH) ₂ , manufactured by Kyowa Chemical Co., Ltd.) having a volume average particle size of 700 nm is well dispersed in 40.0 g of cyclohexanone. To the solution, 0.12 g of 3-aminopropyltrimethoxysilane (silane coupling agent, manufactured by Chisso Corporation) was added and reacted at 65 ° C. for 30 minutes. Thereafter, 7.6 g of styrene (manufactured by Kanto Chemical Co., Ltd.), 9.5 g of the compound obtained in Synthesis Example 2, and 0.08 g of azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) as an initiator were added. , And reacted at 70 ° C. for 15 hours.
After completion of the reaction, unreacted monomer, and Mg (OH) ₂ particle surface to remove polymer not chemically bonded, Mg (OH) washing the ₂ particles in THF, was repeated four times suction filtration. After washing, when the IR spectrum of the particles was measured by FT-IR8900 ((Ltd.) manufactured by Shimadzu Corporation), absorption derived from a carboxylic acid in the vicinity of 1720 cm ^-1 is absorption from the benzene ring in the vicinity of 700 cm ^-1, 2200 cm ^Since absorption derived from a carbodiimide group appeared in the vicinity of ⁻¹ , it was confirmed that a polymer layer containing a carbodiimide group was formed on Mg (OH) ₂ particles.

[Example 5]
In a 100 ml three-necked flask, 10.0 g of Mg (OH) ₂ (Kisuma 5Q: surface untreated Mg (OH) ₂ , manufactured by Kyowa Chemical Co., Ltd.) having a volume average particle size of 700 nm is well dispersed in 40.0 g of cyclohexanone. Into the solution, 1.5 g of diphenylmethane-4,4-diisocyanate (manufactured by Down Chemical Japan Co., Ltd., hereinafter abbreviated as MDI), 0.04 g of p-cat, and phenyl isocyanate (Tokyo Chemical Industry) 0.2 g) was added and heated at 100 ° C. for about 3 hours.
After completion of the reaction, unreacted monomer, and Mg (OH) ₂ particle surface to remove polymer not chemically bonded, Mg (OH) washing the ₂ particles in THF, was repeated four times suction filtration. After washing, when the IR spectrum of this particle was measured with FT-IR8900 (manufactured by Shimadzu Corporation), absorption derived from a carbodiimide group appeared in the vicinity of 2200 cm ⁻¹ , so that the polymer layer containing a carbodiimide group was It was confirmed that it was formed on silica particles.

[Example 6]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Thereafter, Al (OH) ₃ particles having a carbodiimide compound chemically bonded to the surface were synthesized in the same manner as in Example 1.

[Example 7]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Thereafter, Al (OH) ₃ particles having a carbodiimide compound chemically bonded to the surface were synthesized in the same manner as in Example 2.

[Example 8]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Thereafter, Al (OH) ₃ particles having a polymer layer in which a carbodiimide compound was grafted to a styrene-methacrylic acid copolymer were synthesized on the surface in the same manner as in Example 3.

[Example 9]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Thereafter, Al (OH) ₃ particles having a polymer layer containing a carbodiimide group were synthesized in the same manner as in Example 4.

[Example 10]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Thereafter, Al (OH) ₃ particles having a polymer layer containing a carbodiimide group were synthesized in the same manner as in Example 5.

[Comparative Example 1]
In a 100 ml eggplant flask, 60.0 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), Al (OH) ₃ (C301: surface untreated Al (OH) ₃ , Sumitomo Chemical Co., Ltd.) having a volume average particle size of 1.0 μm ) Made) 10.0 g was well dispersed. Subsequently, 0.03 g of 3-aminopropyltriethoxysilane (silane coupling agent, manufactured by Chisso Corporation) was added and stirred at 65 ° C. for 30 minutes.
After completion of the reaction, in order to remove the unreacted silane coupling agent, the Al (OH) ₃ particles were washed with THF and suction filtration was repeated 4 times.
For the Mg (OH) ₂ particles and Al (OH) ₃ particles obtained in Examples 1 to 10 and Comparative Example 1, the thickness of the organic layer on the particle surface and the weight average molecular weight of the polymer forming the surface organic layer (Mw) ) Was obtained by the following method. In addition, the thickness of the organic layer of Mg (OH) ₂ particles (Kisuma 5A, manufactured by Kyowa Chemical Co., Ltd.) that was surface-treated with an organic substance, used in Examples described later, was also obtained. The results are also shown in Table 1.

<Method for measuring weight average molecular weight>
It measured with the gel filtration chromatography (GPC) with the following apparatus and conditions.
Molecular weight measurement conditions GPC measuring device: C-R7A, manufactured by Shimadzu Corporation Detector: UV spectrophotometer detector (SPD-6A), manufactured by Shimadzu Corporation Pump: molecular weight distribution measuring device pump (LC-6AD) , Shimadzu Corporation Column used: Shodex KF804L (Showa Denko Co., Ltd.) 2 and Shodex KF806 (Showa Denko Co., Ltd.) 1 in total 3 connected in series Solvent: Tetrahydrofuran Measurement Temperature: 40 ° C

<Method for measuring thickness of polymer layer>
The density of each particle of Examples 1 to 10 and Comparative Example 1 was determined by a density meter (Accubic 1330, manufactured by Shimadzu Corporation: in a helium atmosphere), and untreated Mg (OH) ₂ particles (Kisuma 5Q) and from the values of al (OH) ₃ (C301) particle density was determined and the volume of the polymer of the inorganic hydroxide 1cm ³ layer, and a volume and total surface area of the inorganic hydroxide 1cm ^3. Using these values, the thickness of the polymer layer was calculated. At this time, the volume and the total surface area were determined on the assumption that the Mg (OH) ₂ particles and the Al (OH) ₃ particles were spherical.

（表１中「０^*」とは、計算の結果、厚みがほぼ０ｎｍであることを意味する。）

("0 ^* " in Table 1 means that the thickness is approximately 0 nm as a result of calculation.)

The particles obtained in Examples 1 to 10 and Comparative Example 1, Kisuma 5A (Comparative Example 2), untreated magnesium hydroxide (Comparative Example 3), and untreated aluminum hydroxide (Comparative Example 4) were mixed with THF, methanol, and methyl ethyl ketone. (MEK, Sanyo Chemicals Co., Ltd.) and a sample dispersed in water of pH 7 were prepared in advance, and the volume average particle size and standard deviation were determined using this.
Specifically, first, each particle of Examples 1 to 10 and Comparative Examples 1 to 4 was added to each of the solvents so as to be 10% by mass, and an ultrasonic disperser (Ultra Turrax T18, Nippon Seiki Co., Ltd.). (Manufactured by Seisakusho) for 30 minutes.
Thereafter, the volume average particle size was measured with a particle size analyzer [MICROTRAC HRA 9320-X100 (measurement range 0.7 μ to 700 μ), manufactured by Nikkiso Co., Ltd.). Table 2 shows the volume average particle size and standard deviation.
Further, the particle diameter (M2) and standard deviation (A2) in THF of Examples 1 to 5 and the particle diameter (M4) and standard deviation (A4) in water were respectively compared with the particle diameter ( M1), standard deviation (A1), particle size in water (M3), value divided by standard deviation (A3), particle size (M2), standard deviation (A2) in THF in Examples 6-10, and water A value obtained by dividing the particle size (M4) and the standard deviation (A4) by the particle size (M1), the standard deviation (A1), the particle size in water (M3), and the standard deviation (A3) in THF of Comparative Example 4, respectively. Are also shown in Table 2.
Furthermore, the particle diameter (M2 ′) and standard deviation (A2 ′) in MEK of Examples 1 to 5, and the particle diameter (M4 ′) and standard deviation (A4 ′) in methanol were compared with the MEK of Comparative Example 3, respectively. Particle diameter (M1 ′), standard deviation (A1 ′), particle diameter in methanol (M3 ′), value divided by standard deviation (A3 ′), particle diameter in MEK of Examples 6 to 10 (M2) '), Standard deviation (A2'), particle size in methanol (M4 '), standard deviation (A4'), particle size (M1 '), standard deviation (A1') in MEK of Comparative Example 4 and Table 2 also shows values divided by the particle diameter (M3 ′) and standard deviation (A3 ′) in methanol.
The standard deviation serves as a guide for the distribution width of the measured particle size distribution, and is a value calculated by the following formula.
Standard deviation = (d84% −d16%) / 2
d84%: Volume average particle diameter at the point where the cumulative curve is 84% (micrometer)
d16%: Volume average particle diameter at the point where the cumulative curve is 16% (micrometer)

The same operation is performed except that the particles of Examples 1 to 10 and Comparative Examples 1 to 4 are added to THF so as to be 30% by mass, the volume average particle diameter and the standard deviation are measured, and further obtained by the following formula. The volume average particle size ratio was determined. The results are shown in Table 3.
Volume average particle size ratio (30)
= Volume average particle diameter at the time of addition of 30% by mass / 10 Volume average particle diameter at the time of addition of 10% by mass

The same operation is performed except that the particles of Examples 1 to 10 and Comparative Examples 1 to 4 are added to THF so as to be 50% by mass, and the volume average particle diameter and the standard deviation are measured. The volume average particle size ratio was determined. The results are shown in Table 4.
Volume average particle size ratio (50)
= Volume average particle diameter at the time of addition of 50% by mass / 10 Volume average particle diameter at the time of addition of 10% by mass

測定不可：粒子が凝集し測定不能

Unmeasurable: Particles cannot be measured due to aggregation

The same operation is performed except that the particles of Examples 1 to 10 and Comparative Examples 1 to 4 are added to THF so as to be 60% by mass, and the volume average particle diameter and the standard deviation are measured. The volume average particle size ratio was determined. The results are shown in Table 5.
Volume average particle size ratio (60)
= Volume average particle diameter at 60 mass% addition / 10 volume average particle diameter at 10 mass% addition

測定不可：粒子が凝集し測定不能

Unmeasurable: Particles cannot be measured due to aggregation

As shown in Tables 3 to 5 above, the flame retardant of the present invention was added not only 10% by mass but also 30% by mass, 50% by mass, and further 60% by mass or more when THF was used as a dispersion medium. Even in this case, it is possible to obtain dispersion characteristics such as the above-described volume average particle diameter and standard deviation. In addition, the same tendency as THF was obtained when MEK and toluene (manufactured by Sanyo Chemicals Co., Ltd.) were used as a dispersion solvent and a flame retardant of 30% by mass, 50% by mass, or 60% by mass or more was added. .
In this way, a highly filled dispersion can be obtained in a highly dispersed state while suppressing an increase in viscosity and aggregation, thereby further improving the high filling, moldability, physical properties after molding, etc. for the organic resin during molding. It is also a great feature of the present invention.

[2] Preparation of inorganic-organic composite flame retardant composition (molded body) [Examples 11 to 20 and Comparative Examples 5 to 12]
Mg (OH) ₂ particles synthesized in Example 1 (Example 11) 4.61 g, Mg (OH) ₂ particles synthesized in Example 2 (Example 12) 4.65 g, Mg (OH) synthesized in Example 3 OH) ₂ particles (Example 13) 4.66 g, Mg (OH) ₂ particles synthesized in Example 4 (Example 14) 4.66 g, Mg (OH) ₂ particles synthesized in Example 5 (Example 15) 4.61 g, Al (OH) ₃ particles synthesized in Example 6 (Example 16) 4.61 g, Al (OH) ₃ particles synthesized in Example 7 (Example 17) 4.65 g, Example 8 in synthesized Al (OH) ₃ particles (example 18) 4.66 g, synthesized Al (OH) ₃ particles in example 9 (example 19) 4.66 g, Al synthesized in example 10 (OH) ₃ particles (example 20) 4.61 g, commercially available surface treatment is Mg (OH) ₂ (Kisuma 5A Kyowa Chemical Co., Ltd.) (Comparative Example 5) 4.50 g, untreated Mg (OH) ₂ (Kisuma 5Q, Kyowa Chemical Co., Ltd.) (Comparative Example 6) 4.50 g, surface treated with Comparative Example 1 Al (OH) ₃ (Comparative Example 9) 4.50 g, untreated Al (OH) ₃ (C301, manufactured by Sumitomo Chemical Co., Ltd.) (Comparative Example 10) 4.50 g each dispersed in 4 g of THF , Epoxy resin (Epeakron N-740, manufactured by Dainippon Ink & Chemicals, Inc.) 3.60 g and a curing agent (Novacure HX3722, manufactured by Asahi Kasei Co., Ltd.) 0.90 g are added to a resin and mixed with inorganic- An organic composite flame retardant composition was prepared.
In addition, 4.50 g of untreated Mg (OH) ₂ (Kisuma 5Q) (Comparative Example 7) and 4.50 g of surface-treated Mg (OH) ₂ (Kisuma 5A) (Comparative Example 8) were added to the Mg of Example 1 respectively. Add 0.11 g of carbodiimide compound synthesized from TDI in the same amount as the carbodiimide-containing organic layer on the surface of (OH) ₂ particles, and add 4.50 g of untreated Al (OH) ₃ (C301) (Comparative Example 11) The same amount of poly TDI (0.11 g) as that of the polymer layer of Example 6 was added to 4.50 g of Al (OH) ₃ (Comparative Example 12) synthesized in 1 to prepare a composition in the same manner as above.

Here, the addition amounts of Mg (OH) ₂ and Al (OH) ₃ in each Example and Comparative Example are based on the following calculation method, and the virgin Mg (OH) ₂ and Al ( OH) ₃ was made equal.
The density of 5 g of Mg (OH) ₂ , Kisuma 5A, and Kisma 5Q synthesized in Example 1 was measured using a density meter (Accubic 1330, manufactured by Shimadzu Corporation: in a helium atmosphere). As a result, Kisuma 5A, Kisuma 5Q is 2.39 g / cm ^3, the synthesized Mg (OH) ₂ in Example 2 was 2.33 g / cm ^3.
Here, the density of the carbodiimide group-containing organic material subjected to the surface treatment in Example 1 is 1.22 g / cm ³ , and the density of untreated Mg (OH) ₂ (Kisuma 5Q) is 2.39 g / cm ³ . from the following equation holds when the volume of the compound obtained in synthesis example 1 in 1 cm ³ and Xcm, ^3, X is a 0.048cm ^3.
1.22X + 2.39 (1-X) = 2.33

Accordingly, the mass of the compound obtained in Synthesis Example 1 as the surface layer in 1 cm ³ is ^{0.048cm 3 × 1.22g / cm 3 =} 0.059 (g), the mass of Kisuma 5Q is (1 −0.048) cm ³ × 2.39 g / cm ³ = 2.28 (g).
Therefore, the amount of the compound obtained in Synthesis Example 1 bonded to the synthesized Mg (OH) ₂ was 100 × 0.059 (g) /2.28+0.048 (g) = 2.5 (mass%) )
As described above, the equivalent amount of Mg (OH) ₂ contained in 4.51 g of Kisma 5A and Kisma 5Q and 4.61 g of Mg (OH) ₂ synthesized in Example 1 is equivalent.
Examples 2 to 10 The polymer amount of the synthesized Mg (OH) _2, particles, and Al (OH) ₃ particles was also determined by the same method. The polymer amount was 3.3% by mass in Example 2, and Example 3 3.5 mass%, Example 4 3.5 mass%, Example 5 2.5 mass%, Example 6 2.5 mass%, Example 7 3.3 mass%, Example 8 Was 3.5% by mass, Example 9 was 3.5% by mass, and Example 10 was 2.5% by mass.

  About the composition prepared in the said Examples 11-20 and Comparative Examples 5-12, the film was produced by the bar-coat method. This was dried overnight and then cured by heat treatment at 100 ° C. for 1 hour and further at 150 ° C. for 0.5 hour. The cured products were prepared in two thicknesses of about 150 μm and 600 μm for all. About the obtained hardened | cured material, the following characteristic was evaluated. The results are shown in Tables 6-9.

<Formability and physical property evaluation of composition (molded product)>
(1) Formability test Except for the size of the test piece of the cured product, the cured product was evaluated according to the following criteria in accordance with the evaluation method of JIS K 7104.
A: The inorganic hydroxide particles are sufficiently uniformly filled, and the surface of the cured product is smooth (touch, visual)
Δ: The inorganic hydroxide particles are uniformly filled, and there are irregularities on a part of the surface of the cured product. X: The inorganic hydroxide particles are not uniformly filled, and the entire surface of the cured product is irregular.

(2) Mechanical strength test The elastic modulus of the cured product (150 µm) was measured at room temperature using a thermal analysis rheology system (EXTAR600 manufactured by Seiko Instruments Inc.).
(Double-circle): Elastic modulus improved significantly compared with the comparative example 5 (Examples 11-15, Comparative Examples 6-8).
The elastic modulus was significantly improved as compared with Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12).
(Triangle | delta): Compared with the comparative example 5, it was equivalent or slightly improved the elasticity modulus (Examples 11-15, Comparative Examples 6-8)
)
Compared with Comparative Example 9, the elastic modulus was equivalent or slightly improved (Examples 16 to 20, Comparative Examples 10 to 10).
12)
×: Elastic modulus decreased

(3) Dielectric Constant Test The dielectric constant of the cured product (150 μm) was measured at a frequency of 1 GHz at room temperature using a dielectric constant measurement device (4291B Impedance Material Analyzer, manufactured by Agilent Technologies). The untreated Mg (OH) ₂ and Al (OH) ₃ compositions had poor moldability and varied in dielectric constant. Therefore, the average value of 4 places was adopted as the dielectric constant.
○: Dielectric constant decreased as compared with Comparative Example 5 (Examples 11 to 15 and Comparative Examples 6 to 8)
Dielectric constant decreased compared to Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12)
(Triangle | delta): Dielectric constant decreased a little compared with the comparative example 5 (Examples 11-15, Comparative Examples 6-8).
Dielectric constant decreased slightly compared to Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12)
×: Dielectric constant does not decrease

(4) Bending test The cured product (600 μm) was cut into a width of 100 mm and a length of 4 cm, and the maximum point bending stress was measured with a three-point bending tester (Microforce tester, manufactured by Instron Corporation). (Measurement conditions: Port span 10mm Initial load 5g Bending speed 10mm / min)
(Double-circle): The bending stress increased compared with the comparative example 5 (Examples 11-15, Comparative Examples 6-8).
Bending stress increased compared to Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12)
(Triangle | delta): The bending stress increased a little compared with the comparative example 5 (Examples 8-12, comparative examples 8-10).
The bending stress was slightly increased as compared with Comparative Example 9 (Examples 13 and 14, Comparative Example 12).
X: Bending stress does not increase or decreases

In Table 6, the ratio of the physical property values, Mg (OH) with respect to ₂ Comparative Example 5 (commercially available have been surface-treated Mg (OH) _2: Kisuma 5A), the comparative example with respect to Al (OH) ₃ 9 ( This is a value calculated using the data of Al (OH) ₃ ) synthesized in Comparative Example 1 as a reference (denominator).

(5) Acid resistance evaluation (about cured | curing material (150 micrometers) of Examples 11-15 and Comparative Examples 5-8)
The cured product was immersed in a 20% by mass aqueous solution of hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) for 5 minutes and 1 hour, washed with distilled water, dried, and the mass after immersion for each time was measured.
The weight reduction rate (%) was calculated from the respective masses before and after the acid treatment, and the acid resistance was evaluated by the change in the color of the cured product after the acid treatment.
A: Acid resistance x: No acid resistance

(6) Alkali resistance evaluation (for cured products (150 μm) of Examples 16 to 20 and Comparative Examples 9 to 12)
The cured product was immersed in a 50% by weight aqueous solution of potassium hydroxide (manufactured by Sigma Aldrich Co., Ltd.) for 1 hour, washed with distilled water, dried, and the mass after immersion for each time was measured.
The weight reduction rate (%) was calculated from the respective masses before and after the alkali treatment, and the alkali resistance was evaluated by the change in the color of the cured product after the acid treatment.
◎: Alkali resistant x: Alkali resistant

(7) Insulation resistance test In order to measure the insulation reliability of the cured product (150 μm), normal conditions (treatment at a constant temperature and humidity of 20 ° C. and humidity 65%) and boiling treatment (boiling at 100 ° C.) The insulation resistance (MΩ) resistance after immersion in constant temperature water for 2 hours was measured with an insulation resistivity measuring device (HP 4339B High Resistance Meter, manufactured by Hewlett-Packard Japan).
Measurement conditions: Voltage 100V (AC voltage), current 500μA
○: Insulation resistance value decreased by less than 5% △: Insulation resistance value decreased by 5% or more and less than 10% ×: Insulation resistance value decreased by 10% or more

(8) Water Absorption Test The cured product (thickness: 600 μm) was cut into a width of 50 mm and a length of 100 mm, and the test piece was left in a high-temperature bath maintained at 50 ° C. for 24 hours. Then, it cooled to 20 degreeC in the desiccator, and weighed the test piece. Next, after immersing in a container of distilled water at 23 ° C. for 24 hours, the sample was taken out and wiped off with a dry cloth. The test piece after water absorption was weighed within 1 minute.
○: Weight increase rate is less than Comparative Example 5 (Examples 11 to 15 and Comparative Examples 6 to 8)
Weight increase rate is less than Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12)
X: The rate of weight increase is greater than or equal to Comparative Example 5 (Examples 11 to 15 and Comparative Examples 6 to 8).
Weight increase rate is not less than Comparative Example 9 (Examples 16 to 20, Comparative Examples 10 to 12)

(9) Heat resistance test The heat resistance test of the said hardened | cured material (150 micrometers) was done. The weight loss rate when the cured product was held at 200 ° C. for 30 minutes was measured with a TG / DTA autosampler AST-2 (manufactured by Seiko Instruments Inc.). As a result, there was no weight reduction, and no heat resistance degradation due to the surface treatment agent was observed.

[3] Flame retardancy test [Examples 21 to 30 and Comparative Examples 13 to 20]
Mg (OH) ₂ particles synthesized in Example 1 (Example 21), Mg (OH) ₂ particles synthesized in Example 2 (Example 22), Mg (OH) ₂ particles synthesized in Example 3 (Example) Example 23), Mg (OH) ₂ particles synthesized in Example 4 (Example 24), Mg (OH) ₂ particles synthesized in Example 5 (Example 25), untreated Mg (OH) ₂ particles (Kisuma) 5) (Comparative Example 13), surface-treated commercial Mg (OH) ₂ (Kisuma 5A, manufactured by Kyowa Chemical Co., Ltd.) (Comparative Example 14), and Mg (OH) ₂ calculated by 8.3 g respectively. An inorganic-organic composite flame retardant composition was prepared in the same manner as in Example 11 except that the amount used was. Furthermore, untreated Mg (OH) ₂ particles (Kisuma 5Q) (Comparative Example 15), to each of the surface treatment of the Mg (OH) ₂ particles (Kisuma 5A) (Comparative Example 16), Example 1 Mg (OH) ₂ A carbodiimide compound 0.21 g synthesized from the same amount of TDI as the carbodiimide group-containing organic layer on the particle surface was added, and a composition was prepared in the same manner as in Example 11.

On the other hand, Al (OH) ₃ particles synthesized in Example 6 (Example 26), Al (OH) ₃ particles synthesized in Example 7 (Example 27), Al (OH) ₃ particles synthesized in Example 8 (Example 28), Al (OH) ₃ particles synthesized in Example 9 (Example 29), Al (OH) ₃ particles synthesized in Example 10 (Example 30), untreated Al (OH) ₃ particles (C301) (Comparative Example 17), Al (OH) ₃ particles synthesized in Comparative Example 1 (Comparative Example 18) were used except that the amount of Al (OH) ₃ calculated to be 8.3 g was used. In the same manner as in Example 11, an inorganic-organic composite flame retardant composition was prepared. Furthermore, each of the untreated Al (OH) ₃ particles (C301) (Comparative Example 19) and the Al (OH) ₃ particles synthesized in Comparative Example 1 (Comparative Example 20) had the same amount as the polymer layer of Example 6. Poly TDI 0.21g was added and the composition was prepared like Example 11.
About each obtained inorganic-organic composite flame-retardant composition, the cured | curing material about 150 micrometers thick was produced similarly to the above, and the characteristic which performed the flame-retardant test by the following method was evaluated. The results are shown in Table 10.

<Flame retardancy test evaluation>
Except for the thickness of the test piece, the combustion test was evaluated based on the UL94V vertical flame retardant test method (combustion standard for plastic materials). The results were evaluated according to three criteria of 94-V0, 94-V1, and 94-V2 according to the judgment criteria.
◎: Equivalent to 94-V0 ○: Equivalent to 94-V1 △: Equivalent to 94-V2

As shown in Tables 6 to 10, the inorganic of each example formed by blending Mg (OH) ₂ particles having a carbodiimide group-containing organic layer obtained in Examples 1 to 10 and Al (OH) ₃ It can be seen that the organic composite flame retardant composition exhibits excellent values for both moldability and physical properties. In this case, in Examples 21 to 30, since the cured product is filled with Mg (OH) ₂ and Al (OH) ₃ particles in a highly dispersed state, an extremely high flame retardant effect is obtained. Recognize.
On the other hand, from the results of each comparative example, Mg (OH) ₂ particles or Al (OH) ₃ particles that are not chemically bonded to the inorganic surface even though the same amount of organic substance having a carbodiimide group with respect to the inorganic hydroxide is contained. It can be seen that in the blended composition, the effect of improving moldability and physical properties is not obtained.
From the above results, the inorganic hydroxide having a carbodiimide group-containing organic layer has high dispersibility, and at the same time, can suppress a decrease in physical properties that has been a problem in the past when a resin is blended. Therefore, it is possible to sufficiently exhibit the effect of improving flame retardance while preventing the deterioration of physical properties. The inorganic-organic composite flame retardant composition of the present invention is expected to be used in various fields as a composition having high flame retardancy.

Claims (12)

An inorganic hydroxide and a carbodiimide group-containing organic layer chemically bonded to the surface of the inorganic hydroxide;
The said carbodiimide group containing organic layer consists of at least 1 sort (s) of the carbodiimide group containing compound shown by Formula (1), and the carbodiimide group containing compound shown by Formula (2), The flame retardant characterized by the above-mentioned.
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -NCO] l (1)
_{^{(X 1) m -Z- [A-}} (R 1 -N = C = N) n -R 1 -A-Z- (X 2) 3] l (2)
[Wherein R ¹ represents a residue from an isocyanate compound,
X ¹ and X ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may contain an unsaturated structure, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, Or an alkoxy group having 1 to 20 carbon atoms, and when X ¹ and X ² are plural, they may be the same as or different from each other;
Z independently represents a silicon atom or a titanium atom,
A represents a divalent or higher valent organic group containing a bond derived from an isocyanate group,
m and l represent an integer satisfying 1 to 3 and m + 1 = 4,
n represents an integer of 1 to 100. ] Standard deviation (A ₁ ) of particle size distribution of surface untreated inorganic hydroxide and standard deviation of particle size distribution of inorganic hydroxide provided with carbodiimide group-containing organic layer when tetrahydrofuran is used as a dispersion medium The flame retardant according to claim 1, wherein (A ₂ ) satisfies the following formula.
(A ₂ ) / (A ₁ ) ≦ 1.0 When tetrahydrofuran is used as a dispersion medium, the volume average particle size (M ₁ ) of the surface untreated inorganic hydroxide and the volume average particle size (M ₂ ) of the inorganic hydroxide provided with the carbodiimide group-containing organic layer. The flame retardant according to claim 1, wherein:
(M ₂ ) / (M ₁ ) ≦ 1.0 The standard deviation (A ₃ ) of the particle size distribution of the surface untreated inorganic hydroxide and the particle size distribution of the inorganic hydroxide provided with the carbodiimide group-containing organic layer when water at pH 7 is used as the dispersion medium. The flame retardant according to claim 1, wherein the standard deviation (A ₄ ) satisfies the following formula.
(A ₄ ) / (A ₃ )> 1.0 When water having a pH of 7 is used as a dispersion medium, the volume average particle diameter (M ₃ ) of the surface untreated inorganic hydroxide and the volume average particle diameter (M of the inorganic hydroxide provided with the carbodiimide group-containing organic layer) The flame retardant according to claim 1, wherein ₄ ) satisfies the following formula.
(M ₄ ) / (M ₃ )> 1.0   The flame retardant according to claim 1, wherein at least one of the terminal isocyanate groups of the carbodiimide group-containing compound represented by the formula (1) is sealed with a functional group having reactivity with the isocyanate group.   The flame retardant according to claim 6, wherein the functional group having reactivity with the isocyanate group is a hydroxyl group, a primary or secondary amino group, a carboxyl group, or a thiol group.   The flame retardant according to any one of claims 1 to 7, wherein the inorganic hydroxide is a particle having a volume average particle diameter of 1 nm to 100 µm.   The flame retardant according to any one of claims 1 to 8, wherein the carbodiimide group-containing organic layer is lipophilic.   An inorganic-organic composite flame retardant composition comprising the flame retardant according to any one of claims 1 to 9 and an organic resin.   The inorganic-organic composite flame retardant composition according to claim 10, wherein the flame retardant is contained in an amount of 15% by mass or more based on the organic resin. The inorganic-organic composite flame retardant composition according to claim 10 or 11, wherein a total surface area of the flame retardant contained in 1 g of the composition is 2000 cm ² or more.